CN114149678A - Thermosetting resin composition, reinforcing material, metal-clad laminate and use thereof - Google Patents
Thermosetting resin composition, reinforcing material, metal-clad laminate and use thereof Download PDFInfo
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- CN114149678A CN114149678A CN202210023390.9A CN202210023390A CN114149678A CN 114149678 A CN114149678 A CN 114149678A CN 202210023390 A CN202210023390 A CN 202210023390A CN 114149678 A CN114149678 A CN 114149678A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a thermosetting resin composition, a reinforcing material, a metal-clad laminate and application thereof, and relates to the technical field of thermosetting resin, wherein the thermosetting resin composition comprises the following components: the composite material comprises acrylate group terminated polyisobutylene, styrene-isobutylene block copolymer, modified polyphenyl ether, an auxiliary crosslinking agent, an initiator, a flame retardant and an inorganic filler. The invention solves the technical problem that the dielectric property of the electronic substrate material is easy to deteriorate in high-temperature environment and humid environment, and achieves the technical effects of excellent heat resistance and aging resistance while keeping low dielectric property.
Description
Technical Field
The invention relates to the technical field of thermosetting resin, in particular to a thermosetting resin composition, a reinforcing material, a metal-clad laminated plate and application thereof.
Background
In recent years, with the rapid development of electronic information technology, the demand for 400G/800G large-capacity communication has been developed, and it is required to transmit data signals under the condition of higher frequency 56GHz/112GHz, and electronic devices such as a computing module, a communication base station, a server, and a storage device, which are matched with the data signals, are required to perform high-frequency signal transmission.
Since the transmission loss of the electrical signal increases with the increase of the signal transmission frequency, and since the electronic device needs to be applied to different external environments, such as severe environments of high temperature, high humidity, and low temperature, etc., the reliability of signal transmission is reduced, and therefore, better high and low temperature resistance and humidity and heat resistance stability are required in high-frequency and high-speed signal transmission. At present, electronic substrate materials with dielectric stability have become key materials of high frequency and high transmission devices, so as to meet the future demands for high speed information transmission.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
An object of the present invention is to provide a thermosetting resin composition which, after curing, can maintain low dielectric properties while having excellent dielectric stability under high-temperature and moist-heat environments.
The second object of the present invention is to provide a reinforcing material.
It is a further object of the present invention to provide a metal clad laminate.
The invention also aims to provide the application of the metal-clad laminated board in the preparation of a printed circuit board.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a thermosetting resin composition, comprising the following components in parts by mass:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent and 0.1-5 parts of polymerization initiator.
Further, the terminal modifying group of the modified polyisobutylene comprises at least one of alkyl acrylate and alkyl methacrylate;
more preferably, the number average molecular weight of the modified polyisobutene is 5000-50000 g/mol;
further preferably, the modified polyisobutylene has an absolute viscosity of 500 to 5000pa.s at 23 ℃ in an E-type viscometer.
Further, the styrene-isobutylene block copolymer is a diblock or triblock polymer;
more preferably, the mass content of the styrene in the styrene-isobutylene block copolymer is 10-35%;
more preferably, the number average molecular weight of the styrene-isobutylene block copolymer is 50000-100000 g/mol;
further preferably, the styrene-isobutylene block copolymer has an apparent viscosity of 1000 to 5000pa.s at 200 ℃ as measured according to JIS K7199.
Further, the modified polyphenylene ether includes an acrylate-and/or styrene-based-terminated modified polyphenylene ether resin;
more preferably, the number average molecular weight of the acrylate and/or styrene-based end-capped modified polyphenylene ether resin is 500 to 5000 g/mol.
Further, the co-crosslinking agent includes at least one of styrene, divinylbenzene, triallyl isocyanurate, acrylate compounds, methacrylate compounds, and maleimide resins.
Further, the thermosetting resin composition further comprises a flame retardant and an inorganic filler;
the flame retardant comprises at least one of decabromodiphenyl ethane, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bistetrabromophthalimide and tris (tribromophenyl) isocyanurate;
the inorganic filler comprises a low dielectric synthetic spherical silica filler;
the spherical silica filler comprises a spherical silica filler with the surface treated by a silane coupling agent;
the silane coupling agent comprises at least one of a vinyl silane coupling agent, an allyl silane coupling agent, an acrylate silane coupling agent and a methacrylate silane coupling agent;
the dielectric loss of the spherical silicon dioxide filler under the frequency of 10GHz is less than 0.002;
the average particle diameter D50 of the flame retardant and the inorganic filler each independently ranges from 0.5 to 5 μm.
Further, the thermosetting resin composition comprises the following components in parts by weight:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent, 0.1-5 parts of polymerization initiator, 10-40 parts of flame retardant and 50-100 parts of inorganic filler.
In a second aspect, the present invention provides a reinforcing material, which is mainly prepared from the above thermosetting resin composition.
In a third aspect, the present invention provides a metal clad laminate comprising the above-described reinforcement material.
In a fourth aspect, the invention provides a use of the metal-clad laminate in the preparation of a printed circuit board.
Compared with the prior art, the invention has at least the following beneficial effects:
the thermosetting resin composition provided by the invention has excellent curability and better thermosetting effect through synergistic combination of the components and parts by weight thereof, can ensure that the cured resin has excellent heat resistance, excellent weather resistance, higher gas barrier property, low water vapor permeability and low moisture permeability, can fully inhibit the problem of deterioration of the dielectric property in a high-temperature environment and a humid environment, and can maintain the stability of the dielectric property in the humid and hot environment.
In some preferred embodiments, the thermosetting resin composition provided by the present invention, through the synergistic combination of the acrylate-group-terminated polyisobutylene, the styrene-isobutylene block copolymer and the modified polyphenylene ether, not only has excellent curability and can obtain better heat curing effect, but also enables the cured resin to have excellent heat resistance, excellent weather resistance, higher gas barrier property, low water vapor permeability and low moisture permeability, can sufficiently inhibit the problem of deterioration of dielectric properties in high-temperature environment and humid environment, and can maintain the stability of dielectric properties in humid and hot environment.
The reinforced material provided by the invention has the same advantages as the reinforced material obtained after the thermosetting resin composition is cured, and is not repeated.
The metal-clad laminate provided by the present invention has the same advantages as those of the thermosetting resin composition after curing, and is not described herein again.
The metal-clad laminated board provided by the invention has the characteristics of high and low temperature resistance, humidity and heat resistance stability and dielectric stability in the preparation of printed circuit boards.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to a first aspect of the present invention, there is provided a thermosetting resin composition comprising the following components in parts by mass:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent and 0.1-5 parts of polymerization initiator.
The thermosetting resin composition provided by the invention has excellent curability and better thermosetting effect through synergistic combination of the components and parts by weight thereof, can ensure that the cured resin has excellent heat resistance, excellent weather resistance, higher gas barrier property, low water vapor permeability and low moisture permeability, can fully inhibit the problem of deterioration of the dielectric property in a high-temperature environment and a humid environment, and can maintain the stability of the dielectric property in the humid and hot environment.
In the present invention, the modified polyisobutylene refers to a high molecular polymer having a polyisobutylene skeleton and terminated with an alkyl (meth) acrylate, and the terminating group may be one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and isooctyl (meth) acrylate; more preferably, the terminal modifying group of the modified polyisobutylene of the present invention is at least one of methyl acrylate and methyl methacrylate. The polyisobutene molecular chain has excellent low dielectric property, better water vapor barrier property and low water vapor permeability, and can effectively inhibit the problem of material dielectric property deterioration in high-temperature environment and humid environment; the acrylate group at the end of the molecular chain of the modified polyisobutylene has excellent curability, and can react with unsaturated olefin to realize better curing effect.
In a preferred embodiment, the acrylate-based terminated polyisobutylene of the present invention (number average modified polyisobutylene) has a molecular weight of 5000 to 50000g/mol, with typical but non-limiting molecular weights being, for example, 5000g/mol, 6000g/mol, 8000g/mol, 12000g/mol, 14000g/mol, 16000g/mol, 20000g/mol, 25000g/mol, 30000g/mol, 35000g/mol, 40000g/mol, 45000g/mol, 50000 g/mol; the absolute viscosity of the acrylate group-terminated polyisobutylene of the present invention at 23 ℃ in an E-type viscometer is 500 to 5000pa.s, and typical but not limiting absolute viscosity thereof at 23 ℃ in an E-type viscometer is, for example, 500pa.s, 800pa.s, 1000pa.s, 1500pa.s, 2000pa.s, 2500pa.s, 3000pa.s, 3500pa.s, 4000pa.s, 4500pa.s, 5000pa.s, preferably 1000 to 4000 pa.s.
Specific examples of the modified polyisobutylene of the present invention include, but are not limited to, EP400V and EP450A of EPION series manufactured by KANEKA, K.K.K..
In the present invention, the styrene-isobutylene block copolymer is a diblock or triblock polymer having structural formulas represented by formulas (1) and (2), and m and n are the numbers of repeating units of styrene and isobutylene, respectively:
the styrene-isobutylene block copolymer has the characteristics of good low dielectric property, higher glass transition temperature and better high-temperature aging resistance compared with the conventional SBR, better moisture permeability and excellent low moisture permeability, and stable dielectric property in a damp and hot environment.
In a preferred embodiment, the styrene-isobutylene block copolymer of the present invention has a number average molecular weight of 50000 to 100000g/mol, and typical but non-limiting number average molecular weights thereof are, for example, 50000g/mol, 60000g/mol, 70000g/mol, 80000g/mol, 90000g/mol, 100000 g/mol; the styrene-isobutylene block copolymer of the present invention has an apparent viscosity of 1000 to 5000pa · s at 200 ℃ as measured in accordance with JIS K7199 test standard, within which sufficient adhesion can be secured while being more suitable for processability, and typical but not limiting apparent viscosities thereof are, for example, 1000pa · s, 2000pa · s, 3000pa · s, 4000pa · s, 5000pa · s; the styrene-isobutylene block copolymer of the present invention has a styrene content of 10 to 35% and a typical but non-limiting styrene mass percentage content of, for example, 10%, 15%, 20%, 25%, 30%, 35%, and if the ratio of the styrene block mass content in the styrene-isobutylene block copolymer is less than 10%, it may result in low cohesion of the product, and if the ratio of the styrene block mass is more than 35%, it may result in lack of sufficient adhesion.
Specific examples of the styrene-isobutylene block copolymer of the present invention include, but are not limited to, products such as SIBSTAR series 073T, 103T, 107T, which are trade names manufactured by KANEKA corporation, and IBS available from BASF.
In the present invention, the modified polyphenylene ether includes, but is not limited to, acrylate and/or styrene-based end-capped modified polyphenylene ether resins; the number average molecular weight of the acrylate-and/or styrene-based-end-capped modified polyphenylene ether resin of the invention is 500 to 5000g/mol, and more preferably 1000 to 4000g/mol, and typical, but not limiting examples thereof are 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, 3000g/mol, 3500g/mol, 4000g/mol, and 5000 g/mol.
The acrylate and/or styrene-based terminated modified polyphenyl ether resin disclosed by the invention is matched with acrylate-based terminated polyisobutylene and a styrene-isobutylene block copolymer, so that a better heat curing effect can be obtained, the cured resin has good heat resistance, reliability and excellent mechanical property, and meanwhile, good adhesive property is provided for metal-clad foils.
As specific examples of the modified polyphenylene ether of the present invention, SA9000 of Sabic, Inc. can be cited as the methacrylate-terminated modified polyphenylene ether resin, and OPE1200-2st and OPE2200-2st of Asahi Kasei Co., Ltd.
In a preferred embodiment, the co-crosslinking agent of the present invention includes an unsaturated functional group-containing co-crosslinking agent, which means a component having an unsaturated functional group capable of undergoing a crosslinking reaction with the modified polyisobutylene and the modified polyphenylene ether resin to form a three-dimensional network structure.
The co-crosslinking agent of the present invention includes, but is not limited to, at least one of styrene, divinylbenzene, triallyl isocyanurate, acrylate compounds, methacrylate compounds, and maleimide resins.
The selected auxiliary crosslinking agent can realize better curing effect of the thermosetting resin composition components so as to further enhance the performance of the material. In the present invention, in order to give a high crosslinking density to the resin composition after curing, a polyfunctional crosslinking agent is preferably used.
In a preferred embodiment, the polymerization initiator of the present invention includes, but is not limited to, at least one of azobisisobutyronitrile, azobis (2-isopropyl) butyronitrile, azobis-hexanedicarboxonitrile, dibenzoyl peroxide, dimethylbenzyl peroxide, dicumyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxide, benzoic acid peroxide, t-butyl peroxide, butylbenzoic acid peroxide, and t-butylbenzoic acid peroxide.
The polymerization initiator selected in the present invention is effective in promoting the polymerization reaction between the thermosetting resin compositions.
In a preferred embodiment, the thermosetting resin composition of the present invention further comprises a flame retardant and an inorganic filler.
The flame retardant of the present invention includes, but is not limited to, at least one of decabromodiphenylethane, decabromodiphenylether, octabromodiphenylether, ethylenebistetrabromophthalimide, tris (tribromophenyl) isocyanurate, and brominated styrene.
The bromine-containing flame retardant used in the present invention imparts better moisture resistance, dielectric properties and copper foil adhesion to the cured material. The addition amount of the flame retardant is 10-40 parts, the addition amount of the flame retardant can ensure that the material has good flame retardance, and the selection range of the average particle size D50 of the flame retardant is 0.5-5 mu m.
The inorganic filler comprises a low dielectric synthetic spherical silica filler, the spherical silica filler subjected to surface treatment is preferably the spherical silica filler subjected to surface treatment by a vinyl or allyl or (methyl) acrylate silane coupling agent, and the dielectric property of the filler can be improved; the spherical silica filler of the present invention has a dielectric loss of less than 0.002 at a frequency of 10GHz and an average particle diameter D50 of preferably 0.5 to 5 μm.
In a preferred embodiment, the thermosetting resin composition of the present invention comprises the following components in parts by mass:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent, 0.1-5 parts of polymerization initiator, 10-40 parts of flame retardant and 50-100 parts of inorganic filler.
Typical but non-limiting parts by weight of the modified polyisobutene are, for example, 3 parts, 10 parts, 15 parts, 20 parts, 25 parts; typical but non-limiting parts by weight of the styrene-isobutylene block copolymer are, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts; typical but non-limiting parts by weight of the modified polyphenylene ether are, for example, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts; typical but non-limiting parts by weight of the co-crosslinking agent are, for example, 3 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts; typical but non-limiting parts by weight of the polymerization initiator are for example 0.1 parts, 2 parts, 3 parts, 4 parts, 5 parts; typical but non-limiting parts by weight of flame retardant are for example 10 parts, 20 parts, 30 parts, 40 parts; typical but non-limiting parts by weight of the inorganic filler are, for example, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts.
The thermosetting resin composition of the invention has excellent curability and better thermosetting effect through the synergistic combination of the components and the parts by weight thereof, can ensure that the cured resin has excellent heat resistance, excellent weather resistance, higher gas barrier property, low water vapor permeability and low moisture permeability, can fully inhibit the problem of deterioration of the dielectric property in a high-temperature environment and a humid environment, and can maintain the stability of the dielectric property in the humid and hot environment.
In the present invention, a method for preparing a thermosetting resin composition, comprising the steps of:
dissolving a styrene-isobutylene block copolymer and modified polyphenyl ether resin in a toluene solvent, respectively adding polyisobutylene terminated by a terminal acrylate group and an auxiliary crosslinking agent after dissolving, stirring and mixing uniformly, then adding a flame retardant, an inorganic filler and an initiator, and performing dispersion treatment to obtain the thermosetting resin composition.
The preparation method of the thermosetting resin composition provided by the invention has the characteristics of simple process and high excellent rate.
According to a second aspect of the present invention, there is provided a reinforcing material prepared mainly from the above thermosetting resin composition.
The reinforcing materials of the present invention include, but are not limited to, prepregs and prepregs.
In the invention, a prepreg obtained by dipping a fabric into the thermosetting resin composition is heated and dried to obtain a prepreg, and the preparation steps comprise: and (3) soaking the fabric into the thermosetting resin composition, soaking the fabric through low-dielectric electronic grade glass fiber cloth, and then heating and drying the fabric at the temperature of 110-150 ℃ to obtain a prepreg.
The reinforced material provided by the invention has the same advantages as the reinforced material obtained after the thermosetting resin composition is cured, and is not repeated.
According to a third aspect of the present invention there is provided a metal clad laminate comprising the reinforcement material described above.
In the present invention, a metal foil and the prepreg (reinforcing material) are stacked and subjected to vacuum hot pressing to obtain a metal-clad laminate.
The metal-clad laminate is prepared by overlapping a conductive foil and the prepreg and pressing at high temperature, wherein the average surface roughness of the conductive foil is less than 3 mu m, and the surface of the conductive foil is treated by a silane coupling agent.
The metal-clad laminate provided by the present invention has the same advantages as those of the above-described cured resin, and will not be described herein again.
According to a fourth aspect of the present invention there is provided the use of a metal clad laminate as described above in the manufacture of a printed circuit board.
The multilayer printed wiring board (printed circuit board) is manufactured by matching the prepreg and the metal clad laminate and performing interlayer wiring, wherein the loss factor Df of the metal clad laminate at 10GHz is less than or equal to 0.002, and the dielectric constant Dk at 10GHz is less than 3.4.
The metal-clad laminated board provided by the invention has the characteristics of high and low temperature resistance, humidity and heat resistance stability and dielectric stability in the preparation of printed circuit boards.
The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.
Example 1
The thermosetting resin composition comprises the following components in parts by weight, and the use amount of each component is shown in Table 1:
10 parts of a modified polyisobutylene (trade name: EP400V, acrylate group-terminated polyisobutylene having a number average molecular weight of 17000g/mol, molecular weight distribution PDI of 1.2 and viscosity of 3500Pa.s/23 ℃ C., manufacturer: Kaneka), 20 parts of a styrene-isobutylene block copolymer (trade name: SIBS 103T having a number average molecular weight of 100000g/mol, styrene content of 30% and viscosity of 4000Pa.s/200 ℃ C., manufacturer: Kaneka), 60 parts of a modified polyphenylene ether resin (trade name: SA9000, methacrylate group-terminated modified polyphenylene ether having a number average molecular weight of 2300g/mol, manufacturer: Sabic), 10 parts of co-crosslinking agent (L-DAIC, manufacturer: four nations chemical), 0.5 part of polymerization initiator (Prehexa 25B, manufacturer Arkema), 25 parts of flame retardant (8010, manufacturer: Yabao), and 65 parts of inorganic filler (EQ2410SCB, manufacturer: three hours).
Example 2
The thermosetting resin composition comprises the following components in parts by weight, and the use amount of each component is shown in Table 1:
15 parts of modified polyisobutylene (trade name: EP400V, manufacturer: Kaneka, same as in example 1), 15 parts of styrene-isobutylene block copolymer (trade name: SIBS 103T, manufacturer: Kaneka, same as in example 1), 60 parts of modified polyphenylene ether resin (trade name: SA9000, manufacturer: Sabic, same as in example 1), 10 parts of co-crosslinking agent (L-DAIC, manufacturer: Quadrature chemical), 0.5 part of polymerization initiator (Prehexa 25B, manufacturer Arkema), 25 parts of flame retardant (8010, manufacturer: Yabao), and 65 parts of inorganic filler (EQ2410SCB, manufacturer: Times).
Example 3
The thermosetting resin composition comprises the following components in parts by weight, and the use amount of each component is shown in Table 1:
10 parts of modified polyisobutylene (trade name: EP400V, manufacturer: Kaneka, same as in example 1), 15 parts of styrene-isobutylene block copolymer (trade name: SIBS 103T, manufacturer: Kaneka, same as in example 1), 65 parts of modified polyphenylene ether resin (trade name: SA9000, manufacturer: Sabic, same as in example 1), 9 parts of co-crosslinking agent (L-DAIC, manufacturer: Quadrature chemical), 0.5 part of polymerization initiator (Prehexa 25B, manufacturer Arkema), 25 parts of flame retardant (8010, manufacturer: Yabao), and 65 parts of inorganic filler (EQ2410SCB, manufacturer: Times).
Example 4
The thermosetting resin composition comprises the following components in parts by weight, and the use amount of each component is shown in Table 1:
7 parts of modified polyisobutylene (trade name: EP400V, manufacturer: Kaneka, same as in example 1), 13 parts of styrene-isobutylene block copolymer (trade name: SIBS 103T, manufacturer: Kaneka, same as in example 1), 70 parts of modified polyphenylene ether resin (trade name: SA9000, manufacturer: Sabic, same as in example 1), 10 parts of co-crosslinking agent (L-DAIC, manufacturer: Quadrature chemical), 0.5 part of polymerization initiator (Prehexa 25B, manufacturer Arkema), 25 parts of flame retardant (8010, manufacturer: Yabao), and 65 parts of inorganic filler (EQ2410SCB, manufacturer: Times).
Example 5
The method for preparing the thermosetting resin compositions of examples 1 to 4, comprising the steps of:
a styrene-isobutylene block copolymer (trade name: SIBS 103T, manufacturer: Kaneka) and a modified polyphenylene ether resin (trade name: SA9000, manufacturer: Sabic) were first dissolved in a toluene solvent, and then a modified polyisobutylene (trade name: EP400V, manufacturer: Kaneka) and a co-crosslinking agent (L-DAIC, manufacturer: Quadrature chemical) were added and mixed well, followed by adding a flame retardant (8010, manufacturer: Yabao), an inorganic filler (EQ2410SCB, manufacturer: Sanger) and a polymerization initiator (Prehexa 25B, manufacturer Arkema), followed by dispersion treatment to obtain a thermosetting resin composition.
Comparative example 1
This comparative example is different from example 1 in that unsaturated polybutadiene B3000 (manufacturer: Japan Caoda) was used in place of the modified polyisobutylene in example 1, 15 parts by mass of B3000, a triblock copolymer A1535 of styrene ethylene-butadiene (manufacturer: Kraton) was used in place of the styrene-isobutylene block copolymer in example 1, 15 parts by mass of A1535, the other components and parts by weight thereof were the same as those in example 1, the amounts of the components are shown in Table 1, and a thermosetting resin composition was obtained in the same manner as in example 1.
Comparative example 2
This comparative example is different from example 1 in that unsaturated polybutadiene B3000 (manufacturer: Gray Valley) was used in place of the modified polyisobutylene in example 1, the mass part of B3000 was 30 parts, the styrene-isobutylene block copolymer in example 1 was not added in this comparative example, other components and parts by weight thereof were the same as in example 1, the amounts of the components are shown in Table 1, and the preparation method is the same as in example 1, to obtain a thermosetting resin composition.
Comparative example 3
This comparative example is different from example 1 in that the modified polyisobutylene of example 1 was not added, and the styrene-isobutylene block copolymer of example 1 was replaced with a styrene ethylene-butadiene triblock copolymer A1535 (manufacturer: Kraton), the mass part of A1535 was 30 parts, the other components and the parts by weight thereof were the same as in example 1, the amounts of the components are shown in Table 1, and a thermosetting resin composition was obtained in the same manner as in example 1.
Comparative example 4
This comparative example is different from example 1 in that the modified polyphenylene ether resin of example 1 was not added, the other components and the parts by weight thereof were the same as in example 1, the amounts of the components are shown in Table 1, the preparation method is the same as in example 1, and a thermosetting resin composition was obtained.
Comparative example 5
This comparative example is different from example 1 in that it replaces the modified polyphenylene ether resin of example 1 with the same amount of Xyron S201A (manufacturer: Asahi-Kasei, unmodified polyphenylene ether resin), the other components and parts by weight thereof are the same as those of example 1, the amounts of the components are shown in Table 1, and the preparation method is the same as that of example 1 to obtain a thermosetting resin composition.
TABLE 1
Test examples
The thermosetting resin compositions obtained in examples 1 to 4 and comparative examples 1 to 4 were heat-cured to obtain cured products (the composition of comparative example 5 was not cured and molded and thus was not tested), and the following tests were further carried out, the data of which are shown in Table 2:
glass transition temperature (Tg): the peak of tan delta curve is Tg as determined by the DMA test method specified in IPC-TM-6502.4.24.4 using DMA instrument test.
Testing high and low temperature storage modulus: the storage modulus data at-50 ℃ and 150 ℃ are respectively obtained by using a DMA instrument test and measuring according to a DMA test method specified by IPC-TM-6502.4.24.4.
Dielectric property at normal temperature: the dielectric constant Dk and the dielectric dissipation factor Df were measured at room temperature at 25 ℃ in accordance with the test method specified in IPC-TM-6502.5.5.9.
High temperature dielectric properties: the dielectric constant Dk and dielectric dissipation factor Df were tested at a high temperature of 100 ℃ according to the test method specified in IPC-TM-6502.5.5.9.
High temperature high humidity dielectric properties: the dielectric constant Dk and dielectric loss factor Df are tested after standing for 96hr in a constant temperature and humidity machine at 85 deg.C/90% RH temperature and humidity according to the test method specified by IPC-TM-6502.5.5.9.
Aging resistance: the laminate was made into tensile bars and the tensile strength of the bars was measured after aging in an oven at 150 ℃ for 14 days, and the aging resistance was characterized by the retention of tensile strength.
Moisture absorption: placing the standard sample in pure water at 25 deg.C, and measuring sample mass after 24hr, wherein the moisture absorption rate is sample mass difference before and after moisture absorption/sample mass before moisture absorption.
Heat resistance: t300: the samples were tested for delamination time at 300 ℃ using TMA instrumentation and determined according to the test method specified in IPC-TM-6502.4.24.1.
PCT: autoclave retort test the laminate was subjected to a retort test at 120 c and measured according to the test method specified by IPC-TM-6502.6.16.
TABLE 2
As can be seen from table 2, the thermosetting resin compositions provided in examples 1 to 4 of the present invention have excellent heat resistance, excellent weather resistance, low permeability, and higher moisture barrier property after curing, and also stably maintain lower dielectric properties in a hot and humid environment, compared to the thermosetting resin compositions provided in comparative examples 1 to 4.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The thermosetting resin composition is characterized by comprising the following components in parts by mass:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent and 0.1-5 parts of polymerization initiator.
2. The thermosetting resin composition of claim 1, wherein the terminal modifying group of the modified polyisobutylene comprises at least one of an alkyl acrylate and an alkyl methacrylate;
preferably, the number average molecular weight of the modified polyisobutene is 5000-50000 g/mol;
preferably, the modified polyisobutylene has an absolute viscosity of 500 to 5000pa.s at 23 ℃ in an E-type viscometer.
3. The thermosetting resin composition of claim 1, wherein the styrene-isobutylene block copolymer is a di-block or tri-block polymer;
preferably, the mass content of the styrene in the styrene-isobutylene block copolymer is 10-35%;
preferably, the number average molecular weight of the styrene-isobutylene block copolymer is 50000-100000 g/mol;
preferably, the styrene-isobutylene block copolymer has an apparent viscosity of 1000 to 5000pa · s at 200 ℃ as measured according to JIS K7199 standard.
4. The thermosetting resin composition claimed in claim 1, wherein the modified polyphenylene ether comprises an acrylate and/or styrene-based capped modified polyphenylene ether resin;
preferably, the acrylate and/or styrene-based end-capped modified polyphenylene ether resin has a number average molecular weight of 500 to 5000 g/mol.
5. The thermosetting resin composition of claim 1, wherein the co-crosslinking agent comprises at least one of styrene, divinylbenzene, triallyl isocyanurate, acrylate compounds, methacrylate compounds, and maleimide resins.
6. The thermosetting resin composition according to claim 1, further comprising a flame retardant and an inorganic filler;
the flame retardant comprises at least one of decabromodiphenyl ethane, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bistetrabromophthalimide and tris (tribromophenyl) isocyanurate;
the inorganic filler comprises a low dielectric synthetic spherical silica filler;
the spherical silica filler comprises a spherical silica filler with the surface treated by a silane coupling agent;
the silane coupling agent comprises at least one of a vinyl silane coupling agent, an allyl silane coupling agent, an acrylate silane coupling agent and a methacrylate silane coupling agent;
the dielectric loss of the spherical silicon dioxide filler under the frequency of 10GHz is less than 0.002;
the average particle diameter D50 of the flame retardant and the inorganic filler each independently ranges from 0.5 to 5 μm.
7. The thermosetting resin composition according to any one of claims 1 to 6, characterized in that it comprises the following components in parts by mass:
3-25 parts of modified polyisobutylene, 5-35 parts of styrene-isobutylene block copolymer, 30-80 parts of modified polyphenylene oxide, 3-30 parts of auxiliary crosslinking agent, 0.1-5 parts of polymerization initiator, 10-40 parts of flame retardant and 50-100 parts of inorganic filler.
8. A reinforcing material prepared mainly from the thermosetting resin composition claimed in any one of claims 1 to 7.
9. A metal clad laminate comprising the reinforcing material of claim 8.
10. Use of the metal-clad laminate of claim 9 in the preparation of printed circuit boards.
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| TWI832554B (en) | 2022-11-14 | 2024-02-11 | 聯茂電子股份有限公司 | Methods for manufacturing solidified body and metal clad substrate |
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